CN114561718A - Composite fiber material, preparation method thereof and high-stretchability fibrous supercapacitor - Google Patents

Composite fiber material, preparation method thereof and high-stretchability fibrous supercapacitor Download PDF

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CN114561718A
CN114561718A CN202210192140.8A CN202210192140A CN114561718A CN 114561718 A CN114561718 A CN 114561718A CN 202210192140 A CN202210192140 A CN 202210192140A CN 114561718 A CN114561718 A CN 114561718A
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composite fiber
ethylenedioxythiophene
fiber material
poly
polystyrene sulfonate
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CN114561718B (en
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马明明
刘蝶
晏秀男
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/48Conductive polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/56Solid electrolytes, e.g. gels; Additives therein
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention provides a composite fiber material which comprises a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer and sodium polyacrylate compounded in the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer. The invention provides a porous structure conductive high-stretchability composite fiber with a specific structure and composition. The invention adopts poly 3, 4-ethylenedioxythiophene polystyrene sulfonate, which is a rigid conjugated polymer with high conductivity, and particularly combines sodium polyacrylate, which is a polymer with high stretchability, and the poly 3, 4-ethylenedioxythiophene polystyrene sulfonate and the polymer are specifically combined. The stretchable supercapacitor provided by the invention simultaneously realizes flexibility, stretchability and higher specific capacitance, and meanwhile, the preparation method is simple, mild in condition and strong in controllability, is more suitable for large-scale popularization, has wide application prospect in the field of stretchable high-performance energy storage devices, and is expected to generate great social value and economic value.

Description

Composite fiber material, preparation method thereof and high-stretchability fibrous supercapacitor
Technical Field
The invention belongs to the technical field of supercapacitors, relates to a composite fiber material and a preparation method thereof, and a supercapacitor, and particularly relates to a composite fiber material and a preparation method thereof, and a fibrous supercapacitor with high stretchability.
Background
Batteries and supercapacitors (SC, a power source with special properties between conventional capacitors and batteries, which mainly stores electric energy by means of electric double layers and redox pseudocapacitance charges, but the energy storage process does not undergo chemical reactions, and is reversible, just because the supercapacitors can be repeatedly charged and discharged for tens of thousands of times) are two most promising energy storage methods. SC has a high power density relative to batteries and a high energy density relative to conventional capacitors. In addition, SC has fast charging and discharging speed, high efficiency, long cycle life, safety and environmental protection, can fill the gap of the traditional energy storage device, and is a novel energy storage device. Supercapacitors rely primarily on electric double layer and redox pseudocapacitive charges to store electrical energy. But no chemical reaction occurs in the process of energy storage, and the energy storage process is reversible, and the super capacitor can be repeatedly charged and discharged for tens of thousands of times. As a novel energy storage device in the aspect of energy storage, the SC has high power density, long cycle life and high charging and discharging speed, the performance of the novel energy storage device is between that of a traditional dielectric capacitor and a battery, the defects of the traditional energy storage device can be overcome, and the novel energy storage device has great application potential.
To meet the next generation of smart wearable devices, new energy storage devices with the capability of stretching, compressing, bending, twisting, and even deforming into arbitrary shapes must be considered and developed. However, the conventional supercapacitor with a two-dimensional planar structure has a large volume and poor flexibility, and cannot meet the recent rapid development of consumer electronics miniaturization and intelligent wearable clothes, so that the development of a wearable and telescopic energy storage unit is particularly important. The flexible SC needs to have the characteristics of self-supporting property, light and portable device, simplified assembly, low production cost, safety and environmental protection, and therefore, the flexible SC is widely researched in the fields of biomedicine, energy storage and conversion devices, wearable equipment, medical sensors, portable equipment and the like.
A general strategy for making stretchable electrodes is to deposit electrochemically active materials, typically rigid materials such as carbon-based materials, metal oxides and composites thereof, on a stretchable substrate, coated on a supporting substrate that is elastic but not electrochemically active such as Polydimethylsiloxane (PDMS) films, Carbon Nanotube (CNT) films, CNTs/PDMS films, elastic fibers and fabrics. Due to the mismatch in stretchability of the electroactive material and the inactive support substrate, thin layers of electroactive material may delaminate from the substrate during charge-discharge cycles or stretch-release cycles, which can result in significant degradation of device performance. On the other hand, in order to load an electroactive material onto a substrate, many complicated steps are required to manufacture an electrode. And the stretchability of the assembled supercapacitor is severely limited by the ability of the substrate to elastically deform. Furthermore, most of these substrates have low conductivity or capacitance, which is not conducive to achieving high energy or power density for supercapacitors. Other technical schemes have been disclosed in the prior art, such as that the Bo Wang project group realizes a high-performance flexible supercapacitor by electrochemically interweaving MOF crystals and conductive polymer Polyaniline (PANI), and the electrode prepared by the method has very high surface capacitance (2146mF cm)-2) However, the capacity retention was not high, and the capacity retention was 80% after 2000 cycles. For another example, the project group of Jikang Yuan also reported that a chemical reduction method based synthesis of hexagonal MnO2And printing the water-based inorganic ink consisting of the nano sheets on commercial A4 paper pretreated by the multi-wall carbon nano tubes to prepare the flexible supercapacitor. The electrode prepared by the method has maximum specific capacitance of 1035F g-1And the capacitance retention rate of 98.9 percent is maintained in 10000 cycles, but the manufacturing process is complicated, and certain difficulty exists in application conversion.
Therefore, how to find a more suitable supercapacitor to better satisfy the next generation of smart wearable devices, which has the functions of stretching, compressing, bending, twisting and even deforming into any shape, has become one of the focuses of great concern of many prospective researchers in the field.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a composite fiber material, a preparation method thereof, and a super capacitor, in particular, a fibrous super capacitor with high stretchability. The composite fiber material provided by the invention combines rigid conductive polymer PEDOT: the PSS and the stretchable polymer PAAS can be used for preparing the super capacitor with excellent stretchability and high specific capacitance, and meanwhile, the preparation method is simple, mild in condition and strong in controllability, is more suitable for large-scale popularization and application, has wide application prospect, and is expected to generate great social value and economic value.
The invention provides a composite fiber material which comprises a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer and sodium polyacrylate compounded in the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer.
Preferably, in the composite fiber material, the mass ratio of the total mass of the poly 3, 4-ethylenedioxythiophene and the polystyrene sulfonate to the mass of the sodium polyacrylate is 1: (0.025 to 0.05);
the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer is a conjugated polymer;
the conjugated polymer includes a rigid conductive conjugated polymer.
Preferably, the composite fiber material is a hydrogel fiber material;
the length of the composite fiber material is 3-30 cm;
the diameter of the composite fiber material is 30-300 mu m;
the compounding includes physical compounding.
Preferably, the composite fibre material has a porous structure;
the aperture of the composite fiber material is 0.25-2 μm;
the composite fiber material is a high-stretchability conductive composite fiber material;
the elongation at break of the composite fiber material is 50-500%;
the conductivity of the composite fiber material is 1000-3000S m-1
The composite fiber material is a water-resistant composite fiber material.
The invention provides a preparation method of a composite fiber material, which comprises the following steps:
1) mixing 3, 4-ethylenedioxythiophene, polystyrene sulfonic acid and water, adding ferric sulfate and sodium persulfate, reacting and washing to obtain poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate composite gel;
2) heating and mixing the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate composite gel obtained in the step, sodium polyacrylate and a solvent to obtain a poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate hydrogel;
3) and (3) carrying out stretch spinning on the poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate hydrogel obtained in the step, and curing to obtain the poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber material.
Preferably, the mass ratio of the 3, 4-ethylenedioxythiophene to the polystyrene sulfonic acid is (0.15-0.25): 1;
the molar ratio of the 3, 4-ethylenedioxythiophene to the ferric sulfate is (1.0-2.0): 1;
the molar ratio of the sodium persulfate to the 3, 4-ethylenedioxythiophene is (0.8-1.5): 1;
the reaction time is 12-24 h;
the washing is specifically to wash until the supernatant is neutral.
Preferably, the solvent comprises one or more of dimethyl sulfoxide, acetone, N-dimethylformamide, acetonitrile, methanol and ethanol;
the heating and mixing temperature is 50-90 ℃;
the heating and mixing time is 20-60 min;
the curing is specifically that the water is evaporated and then cured;
the curing process also comprises acid soaking treatment;
the acid soaking time is 6-24 hours.
The invention provides a super capacitor, which comprises at least 2 wound fiber materials;
the fiber material comprises a composite fiber material and a hydrogel electrolyte coated on the surface of the composite fiber material;
the composite fiber material is the composite fiber material according to any one of the above technical schemes or the composite fiber material prepared by the preparation method according to any one of the above technical schemes.
Preferably, the supercapacitor further comprises a second hydrogel electrolyte layer wrapped on the surface of the wound fiber material;
after the second hydrogel electrolyte layer is wrapped, no gap exists among the 2 wound fiber materials;
the super capacitor also comprises a protective layer coated on the second hydrogel electrolyte layer;
the protective layer is made of one or more of polymethyl acrylate, polybutyl acrylate, polydimethylsiloxane and polyethyl acrylate;
the super capacitor is a fibrous stretchable super capacitor;
the super capacitor comprises an all-solid-state super capacitor.
Preferably, the hydrogel electrolyte comprises a polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte;
the total mass content of hydroquinone and benzoquinone in the hydrogel electrolyte is 0.1-1%;
the preparation method of the polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte comprises the following steps:
mixing p-toluenesulfonic acid, hydroquinone, benzoquinone, water and acetic acid, adding polyvinyl alcohol, heating and mixing to obtain a polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte;
the temperature for heating and mixing is 80-100 ℃;
the preparation method of the supercapacitor comprises the following steps:
soaking two poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate-sodium polyacrylate composite fiber materials in a hydrogel electrolyte, taking out the composite fiber materials, wrapping the two fiber materials when the composite fiber materials are to be dried, compounding the hydrogel electrolyte on the surfaces of the wrapped fiber materials, compounding a protective layer when the composite fiber materials are to be dried, and drying the protective layer to obtain the supercapacitor.
The invention provides a composite fiber material which comprises a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer and sodium polyacrylate compounded in the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer. Compared with the prior art, the invention aims at the existing flexible super capacitor, needs to support the substrate or the elastic substrate, and has the stretchability seriously limited by the elastic deformation capacity of the substrate; the preparation method is complicated and is difficult to produce in large scale; and the elastic substrate has no electrochemical activity, but occupies a large proportion of volume and mass in the stretchable super capacitor, and is not beneficial to realizing the lightness and thinness of the device. The invention is based on the research that the conductive polymer-based hydrogel (CPHs) is one of the feasible directions for preparing the flexible electrode, but the stretchability and the high capacitance retention rate of the super capacitor prepared by using the conductive polymers such as polyaniline and polypyrrole are often not compatible.
Based on the technical scheme, the invention creatively designs the composite fiber material with a specific structure and composition, which is the conductive high-stretchability composite fiber with a porous structure. The invention adopts poly 3, 4-ethylenedioxythiophene polystyrene sulfonate (PEDOT: PSS), which is a rigid conjugated polymer with high conductivity, in particular sodium Polyacrylate (PAAS), which is a polymer with high stretchability, and the two are specifically combined to obtain a composite fiber material, thereby obtaining the Fibrous Stretchable Super Capacitor (FSSC) with high stretchability and high specific capacitance.
The preparation method disclosed by the invention is characterized in that PEDOT, PSS and PAAS are combined to generate conductive polymer hydrogel PEDOT, PSS-PAAS by using a simple method, fiber PEDOT, PSS-PAH is formed by drawing and spinning, and the fiber PEDOT, PSS-PAH is prepared into the fibrous stretchable supercapacitor by post-processing and hydrogel electrolyte wrapping. The invention also provides a preparation method of the PEDOT PSS, which has low cost, the method for preparing the stretchable PEDOT PSS-PAAS conductive hydrogel material is simple, and the fiber prepared by using a manual or automatic spinning method has good stretching orientation, excellent conductivity and good stretching performance, and simultaneously has excellent water resistance and can not swell after being soaked in water for a long time. The PEDOT, PSS-PAAS conductive hydrogel material provided by the invention does not need a flexible substrate material when being used for preparing a supercapacitor, and the stretchable all-solid-state supercapacitor formed by directly stretching, spinning and assembling the PEDOT, PSS-PAAS hydrogel has higher volume specific capacitance and surface capacitance, excellent capacitance retention rate of cyclic charge and discharge, and excellent capacitance retention rate under 100% strain stretching-releasing cycle. Diodes may also be lit through the series super-capacitor, powering a clock, etc. The composite fiber material based on the PEDOT, PSS and PAAS conductive hydrogel provided by the invention combines the rigid conductive polymer PEDOT, PSS and the stretchable polymer PAAS, and has excellent stretchability and a high specific capacitance, and the obtained all-solid stretchable super capacitor simultaneously realizes flexibility, stretchability and a high specific capacitance value, and meanwhile, the preparation method is simple, mild in condition and strong in controllability, is more suitable for large-scale popularization and application, has a wide application prospect in the field of stretchable high-performance energy storage devices, and is expected to generate great social value and economic value.
Experimental results show that the composite fiber material prepared by the invention has excellent conductive performance (3000 Sm)-1) The composite material has good tensile property, the elongation at break can reach 150%, the stress at break can reach 23MPa, and meanwhile, the composite material has excellent water resistance and cannot swell after being soaked in water for a long time. The composite fiber material prepared by PEDOT, PSS-PAAS conductive hydrogel material does not need to be flexible when the super capacitor is preparedThe elastic substrate material is a stretchable all-solid-state supercapacitor formed by directly stretching and spinning PEDOT and PSS-PAAS hydrogel and then assembling. The volume specific capacitance value can reach 67.4F/cm at most3And the surface capacitance can reach 100mF/cm2The capacity retention rate of 8000 times of charge and discharge cycles is more than 99%, and the capacity retention rate reaches 83% when the strain is 100% of stretching-releasing cycles are 1000 times. Diodes may also be lit through the series super-capacitor, powering a clock, etc.
Drawings
FIG. 1 is a graph of PEDOT prepared in example 5 of the present invention: optical microscope photograph of PSS-PAH;
FIG. 2 is a graph of PEDOT prepared in example 5 of the present invention: x-ray diffraction pattern of PSS-PAH;
FIG. 3 is a graph of PEDOT prepared in example 5 of the present invention: scanning electron microscopy of PSS-PAH;
figure 4 is a graph of different PEDOTs prepared according to the invention: PEDOT at PSS doping level: mechanical properties of PSS-PAH;
FIG. 5 shows the composite fiber prepared by the present invention soaked in H2O (left bottle) and 0.1M NaHCO3(right bottle) contrast photograph of 24h swelling at 80 ℃;
fig. 6 is a graph of PEDOT: apparent performance of PSS-PAH Fibrous Stretchable Supercapacitors (FSSC);
FIG. 7 is a result of cyclic voltammetry testing of Fibrous Stretchable Supercapacitors (FSSCs) made according to the present invention;
FIG. 8 is a graph of the result of constant current charge discharge (GCD) testing of Fibrous Stretchable Supercapacitors (FSSCs) made in accordance with the present invention;
FIG. 9 is a cycle stability test of a Fibrous Stretchable Supercapacitor (FSSC) made according to the present invention;
FIG. 10 is an electrochemical performance of a Fibrous Stretchable Supercapacitor (FSSC) made according to the present invention under stretching;
FIG. 11 is a photomicrograph of a Fibrous Stretchable Supercapacitor (FSSC) lighting diode made in accordance with the present invention;
FIG. 12 is a photograph of a clock-powered object with Fibrous Stretchable Supercapacitors (FSSC) made according to the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
All starting materials for the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts analytically pure materials or meets the purity standard related to the field of preparation of supercapacitors.
All the raw materials, sources and abbreviations thereof, of the present invention belong to conventional sources and abbreviations in the art, and are clearly and clearly defined in the field of related uses, and those skilled in the art can obtain the raw materials commercially available or prepared by conventional methods according to the abbreviations and the corresponding uses.
The invention provides a composite fiber material which comprises a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer and sodium polyacrylate compounded in the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer.
In the present invention, in the composite fiber material, the mass ratio of the total mass of the poly 3, 4-ethylenedioxythiophene and polystyrene sulfonate to the sodium polyacrylate is preferably 1: (0.025 to 0.05), more preferably 1: (0.03 to 0.045), more preferably 1: (0.035-0.04).
In the present invention, the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer is preferably a conjugated polymer. Specifically, in the invention, in the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer, because the polystyrene sulfonate is excessive in the preparation process, the proportion of two materials in the polymer is difficult to embody, and the two materials form a conjugated polymer, wherein the poly 3, 4-ethylenedioxythiophene has the conductive effect.
In the present invention, PEDOT: PSS can use the commercial PEDOT: PSS or use of PEDOT synthesized by itself: PSS.
In the present invention, the conjugated polymer preferably includes a rigid conductive conjugated polymer.
In the present invention, the composite fiber material is preferably a hydrogel fiber material.
In the invention, the length of the composite fiber material is preferably 3-30 cm, more preferably 8-25 cm, and more preferably 13-20 cm.
In the invention, the diameter of the composite fiber material is preferably 30-300 μm, more preferably 50-250 μm, and more preferably 50-150 μm.
In the present invention, the compounding preferably includes physical compounding.
In the present invention, the composite fiber material preferably has a porous structure.
In the invention, the pore diameter of the composite fiber material is preferably 0.25-2 μm, more preferably 0.5-1.7 μm, and more preferably 0.8-1.4 μm.
In the present invention, the composite fiber material is preferably a highly stretchable conductive composite fiber material.
In the present invention, the elongation at break of the composite fiber material is preferably 50% to 500%, more preferably 150% to 400%, and still more preferably 250% to 300%.
In the invention, the conductivity of the composite fiber material is preferably 1000-3000S m-1More preferably 1400 to 2600S m-1More preferably 1800 to 2200S m-1
In the present invention, the composite fiber material is preferably a water-resistant composite fiber material.
The invention provides a preparation method of a composite fiber material, which comprises the following steps:
1) mixing 3, 4-ethylenedioxythiophene, polystyrene sulfonic acid and water, adding ferric sulfate and sodium persulfate, reacting and washing to obtain poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate composite gel;
2) heating and mixing the poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate composite gel, sodium polyacrylate and a solvent obtained in the step to obtain a poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate hydrogel;
3) and (3) carrying out stretch spinning on the poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate hydrogel obtained in the step, and curing to obtain the poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber material.
The preparation method comprises the steps of mixing 3, 4-ethylenedioxythiophene, polystyrene sulfonic acid and water, adding ferric sulfate and sodium persulfate, reacting, and washing to obtain the poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate composite gel.
In the invention, the mass ratio of the 3, 4-ethylenedioxythiophene to the polystyrene sulfonic acid is preferably (0.15-0.25): 1, more preferably (0.17 to 0.23): 1, more preferably (0.19 to 0.21): 1.
in the invention, the molar ratio of the 3, 4-ethylenedioxythiophene to the ferric sulfate is preferably (1.0-2.0): 1, more preferably (1.3 to 1.7): 1, more preferably (1.4 to 1.6): 1.
in the present invention, the molar ratio of the sodium persulfate to the 3, 4-ethylenedioxythiophene is preferably (0.8 to 1.5): 1, more preferably (0.9 to 1.4): 1, more preferably (1.0 to 1.3): 1, more preferably (1.1 to 1.2): 1.
in the invention, the reaction time is preferably 12-24 h, more preferably 14-22 h, and more preferably 16-20 h.
In the present invention, the washing is particularly preferably carried out until the supernatant is neutral.
The invention further heats and mixes the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate composite gel obtained in the above steps, sodium polyacrylate and a solvent to obtain the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate hydrogel. Namely PEDOT PSS-PAAS hydrogel.
In the present invention, the solvent preferably includes one or more of dimethyl sulfoxide, acetone, N-dimethylformamide, acetonitrile, methanol and ethanol, and more preferably dimethyl sulfoxide, acetone, N-dimethylformamide, acetonitrile, methanol or ethanol. Specifically, the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate composite gel synthesized in step 1) of the invention is a water-containing gel-like substance, so water can be added or not added in step 2).
In the invention, the heating and mixing temperature is preferably 50-90 ℃, more preferably 55-85 ℃, more preferably 60-80 ℃, more preferably 65-75 ℃, and particularly 60-80 ℃.
In the invention, the heating and mixing time is preferably 20-60 min, more preferably 25-55 min, more preferably 30-50 min, more preferably 35-45 min, and particularly may be 20-40 min.
Finally, the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate hydrogel obtained in the step is subjected to stretch spinning and curing to obtain the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber material.
In the present invention, the curing is particularly preferably performed after evaporation of water.
In the present invention, the curing preferably includes an acid soaking treatment.
In the invention, the time of the acid soaking treatment is preferably 6-24 h, more preferably 9-21 h, more preferably 12-18 h, and particularly 8-16 h.
The invention provides a supercapacitor comprising at least 2 wound fibrous materials.
In the present invention, the fiber material preferably includes a composite fiber material and a hydrogel electrolyte coated on the surface of the composite fiber material
In the present invention, the composite fiber material is preferably the composite fiber material according to any one of the above claims or the composite fiber material prepared by the preparation method according to any one of the above claims.
In the present invention, the supercapacitor preferably comprises a second hydrogel electrolyte layer wrapped on the surface of the wound fibrous material.
In the present invention, after the second hydrogel electrolyte layer is wrapped, there is preferably no space between the 2 entangled fiber materials. Specifically, the hydrogel electrolyte layer is further coated on the surfaces of the 2 wound fiber materials wrapped with hydrogel, so that gaps are avoided between two wound fibers.
In the present invention, the supercapacitor preferably comprises a protective layer coated on the second hydrogel electrolyte layer.
In the present invention, the material of the protective layer preferably includes one or more of polymethyl acrylate, polybutyl acrylate, polydimethylsiloxane, and polyethyl acrylate, and more preferably polymethyl acrylate, polybutyl acrylate, polydimethylsiloxane, or polyethyl acrylate.
In the present invention, the supercapacitor is preferably a fibrous stretchable supercapacitor. Further, the supercapacitor preferably comprises an all-solid-state supercapacitor.
In the present invention, the hydrogel electrolyte preferably includes a polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte.
In the present invention, the total mass content of hydroquinone and benzoquinone in the hydrogel electrolyte is preferably 0.1% to 1%, more preferably 0.3% to 0.8%, and still more preferably 0.5% to 0.6%.
In the present invention, the method for preparing the polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte preferably comprises the following steps:
mixing p-toluenesulfonic acid, hydroquinone, benzoquinone, water and acetic acid, adding polyvinyl alcohol, heating and mixing to obtain the polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte.
In the invention, the temperature of the temperature raising and mixing is preferably 80-100 ℃, more preferably 84-96 ℃, and more preferably 88-92 ℃.
In the present invention, the method for manufacturing the supercapacitor preferably comprises the steps of:
soaking two poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate-sodium polyacrylate composite fiber materials in a hydrogel electrolyte, taking out the composite fiber materials, wrapping the two fiber materials when the composite fiber materials are to be dried, compounding the hydrogel electrolyte on the surfaces of the wrapped fiber materials, compounding a protective layer when the composite fiber materials are to be dried, and drying the protective layer to obtain the supercapacitor.
The invention is a complete and refined integral technical scheme, better ensures the composition and structure of the composite fiber material, ensures the structure of the super capacitor, and further improves the performance of the high-stretchability fibrous super capacitor, and the preparation process of the composite fiber material and the super capacitor can specifically comprise the following steps:
PEDOT: preparation of PSS-PAH super capacitor
The PEDOT provided by the invention: the PSS preparation related process is as follows:
the method comprises the following steps:
(1) dissolving a certain amount of 3, 4-Ethylenedioxythiophene (EDOT) and polystyrene sulfonic acid (PSSH) in a certain amount of water, adding a certain amount of ferric sulfate and sodium persulfate, and stirring at normal temperature. And (4) centrifugally washing the reacted liquid by using distilled water until the supernatant is neutral.
The invention provides PEDOT: the PSS-PAH fiber is prepared by the following steps:
the method comprises the following steps:
(A) taking the obtained PEDOT: PSS and H2Mixing O, dimethyl sulfoxide and sodium Polyacrylate (PAAS), heating and dissolving to obtain PEDOT: PSS-PAAS hydrogel.
(B) Obtaining PEDOT by draw spinning after cooling: and (3) soaking the PSS-PAAS hydrogel fiber by using sulfuric acid for post-treatment to obtain PEDOT: PSS-PAH composite fiber.
The invention provides PEDOT: the preparation related process of the PSS-PAH super capacitor is as follows:
the method comprises the following steps:
(a) and (3) mixing PEDOT: the PSS-PAH is wrapped with hydrogel electrolyte, namely two fibers are wrapped when the fibers are dry.
(b) And coating a layer of hydrogel electrolyte on the wrapped double electrode, soaking the double electrode into a polymethyl acrylate solution when the double electrode is dry, and airing to finish the sealing layer.
Specifically, in the present invention, in the step (a), a self-made PEDOT: the mass fraction of PSS is preferably 40% to 80%, more preferably 60% to 80%.
Specifically, in the invention, the heating and dissolving temperature is preferably 50-90 ℃, more preferably 60-90 ℃, and most preferably 60-80 ℃. The heating time is preferably 20 to 60min, and more preferably 20 to 40 min.
Specifically, in the present invention, the mass fraction of the sulfuric acid soaked in the post-treatment is preferably 40% to 90%, and more preferably 60% to 80%. The soaking time is preferably 6-24 h, and more preferably 8-16 h.
Specifically, in the invention, the content of hydroquinone and benzoquinone in the hydrogel electrolyte is 20-80 mM, and more preferably 40-80 mM. Namely, the total mass content of hydroquinone and benzoquinone in the hydrogel electrolyte is preferably 0.1-1%.
Specifically, in the present invention, the polymethyl acrylate solvent is preferably one or more of ethyl acetate, acetone, dichloromethane, and chloroform. The mass fraction of the polyacrylate compound in the polyacrylate compound solution is preferably 5% to 20%, and more preferably 6% to 15%.
The invention provides a composite fiber material, a preparation method thereof and a high-stretchability fibrous supercapacitor. The composite fiber material with specific structure and composition is a conductive high-stretchability composite fiber with a porous structure. The invention adopts poly 3, 4-ethylenedioxythiophene polystyrene sulfonate (PEDOT: PSS), which is a rigid conjugated polymer with high conductivity, in particular sodium Polyacrylate (PAAS), which is a polymer with high stretchability, and the two are specifically combined to obtain a composite fiber material, thereby obtaining the Fibrous Stretchable Super Capacitor (FSSC) with high stretchability and high specific capacitance.
The preparation method disclosed by the invention is characterized in that PEDOT, PSS and PAAS are combined to generate conductive polymer hydrogel PEDOT, PSS-PAAS by using a simple method, fiber PEDOT, PSS-PAH is formed by drawing and spinning, and the fiber PEDOT, PSS-PAH is prepared into the fibrous stretchable supercapacitor by post-processing and hydrogel electrolyte wrapping. PEDOT used: PSS may be obtained directly using commercially available PEDOT PSS or using self-synthesized PEDOT: PSS. The invention also provides a preparation method of the PEDOT PSS, which has low cost, simple method for preparing the stretchable PEDOT PSS-PAAS conductive hydrogel material, and the fiber prepared by using a manual or automatic spinning method has good stretching orientation, excellent conductive performance, good stretching performance, excellent water resistance and no swelling after being soaked in water for a long time. The PEDOT, PSS-PAAS conductive hydrogel material provided by the invention does not need a flexible substrate material when being used for preparing a supercapacitor, and the stretchable all-solid-state supercapacitor formed by directly stretching, spinning and assembling the PEDOT, PSS-PAAS hydrogel has higher volume specific capacitance and surface capacitance, excellent capacitance retention rate of cyclic charge and discharge, and excellent capacitance retention rate under 100% strain stretching-releasing cycle. Diodes may also be lit through the series super-capacitor, powering a clock, etc. The composite fiber material based on the PEDOT, PSS and PAAS conductive hydrogel provided by the invention combines the rigid conductive polymer PEDOT, PSS and the stretchable polymer PAAS, and has excellent stretchability and a high specific capacitance, and the obtained all-solid stretchable super capacitor simultaneously realizes flexibility, stretchability and a high specific capacitance value, and meanwhile, the preparation method is simple, mild in condition and strong in controllability, is more suitable for large-scale popularization and application, has a wide application prospect in the field of stretchable high-performance energy storage devices, and is expected to generate great social value and economic value.
Results of the experimentThe composite fiber material prepared by the invention has excellent conductive performance (3000 Sm)-1) The composite material has good tensile property, the elongation at break can reach 150%, the stress at break can reach 23MPa, and meanwhile, the composite material has excellent water resistance and cannot swell after being soaked in water for a long time. The composite fiber material prepared from the PEDOT, PSS-PAAS conductive hydrogel material does not need a flexible substrate material when the super capacitor is prepared, and the stretchable all-solid-state super capacitor can be formed by directly stretching, spinning and assembling the PEDOT, PSS-PAAS hydrogel. The volume specific capacitance value can reach 67.4F/cm at most3And the surface capacitance can reach 100mF/cm2The capacity retention rate of 8000 times of charge and discharge cycles is more than 99%, and the capacity retention rate reaches 83% when the strain is 100% of stretching-releasing cycles are 1000 times. Diodes may also be lit through the series super-capacitor, powering a clock, etc.
For further illustration of the present invention, a composite fiber material and a method for preparing the same, and a super capacitor according to the present invention will be described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
In the embodiment, the structure of the fiber is characterized by XRD and SEM, the mechanical performance of the fiber and the supercapacitor is tested by a stretcher, and the electrochemical test of the fiber and the supercapacitor is carried out by a Huachen 660I electrochemical instrument.
The following examples illustrate the invention in detail, including PEDOOT: preparation of PSS, PEDOT: preparation of PSS-PAH fiber, PEDOT: structural characterization of PSS-PAH fibers, PEDOT: PSS-PAH fiber conductivity and tensile properties, PEDOT: testing the tensile property and the electrochemical property of the PSS-PAH super capacitor, and testing the tensile property and the electrochemical property of PEDOT: PSS-PAH super capacitor lighting bulb and application for supplying power for small clock. The scope of the invention is not limited to the examples described below.
Example 1
This example serves to illustrate PEDOT: method for preparing PSS
(1) 0.5g of 3, 4-Ethylenedioxythiophene (EDOT) and 3g of 30 wt% polystyrene sulfonic acid (PSSH) are dissolved in 100mL of water, 50 mu L0.05M of ferric sulfate is added, 1g of sodium persulfate is dissolved in water and then poured into the solution, and the solution is stirred at normal temperature for more than 12 hours.
(2) And (3) repeatedly washing the reacted liquid with distilled water until the supernatant is neutral, thus obtaining the dark blue gel PEDOT: PSS, PEDOT tested by freeze dryer: the PSS content is 1-2%.
Example 2
This example was used for PEDOT: preparation method of PSS-PAH fiber
(1) Taking 2g of PEDOT prepared above: PSS, 0.5g H2O, 0.7g of Dimethylsulfoxide (DMSO) and 0.1g of sodium Polyacrylate (PAAS) were mixed, and the mixture was heated and stirred at 70 ℃ for 30 minutes to obtain PEDOT: PSS-PAAS hydrogel.
(2) The fibers were pulled out of the hydrogel with tweezers and allowed to solidify by evaporation of water, yielding PEDOT: PSS-PAH fiber. Then soaking in 70% sulfuric acid for 12 h.
Example 3
This example was used for PEDOT: preparation method of PSS-PAH fiber
(1) Taking 3g of PEDOT prepared above: PSS, 0.5g H2O, 0.7g of dimethyl sulfoxide (DMSO) and 0.1g of sodium Polyacrylate (PAAS) were mixed, and the mixture was heated and stirred at 70 ℃ for 30 minutes to obtain PEDOT: PSS-PAAS hydrogel.
(2) The fibers were pulled out of the hydrogel with tweezers and allowed to solidify by evaporation of water, yielding PEDOT: PSS-PAH fiber. Then soaking in 70% sulfuric acid for 12 h.
Example 4
This example was used for PEDOT: preparation method of PSS-PAH fiber
(1) Taking 4g of PEDOT prepared above: PSS, 0.5g H2O, 0.9g of dimethyl sulfoxide (DMSO) and 0.1g of sodium Polyacrylate (PAAS) were mixed, and the mixture was heated and stirred at 70 ℃ for 30 minutes to obtain PEDOT: PSS-PAAS hydrogel.
(2) The fibers were pulled out of the hydrogel with tweezers and allowed to solidify by evaporation of water, yielding PEDOT: PSS-PAH fiber. Then soaking in 70% sulfuric acid for 12 h.
Example 5
This example was used for PEDOT: preparation method of PSS-PAH fiber
(1) Taking 4g of PEDOT prepared above: PSS, 0.7g of dimethyl sulfoxide (DMSO) and 0.1g of sodium Polyacrylate (PAAS) were mixed, and stirred at 70 ℃ for 30 minutes to obtain PEDOT: PSS-PAAS hydrogel.
(2) The fibers were pulled out of the hydrogel with tweezers and allowed to solidify by evaporation of water, yielding PEDOT: PSS-PAH fiber. Then soaking in 70% sulfuric acid for 12 h.
Example 6
This example was used for PEDOT: preparation method of PSS-PAH fiber
(1) Taking 4g of PEDOT prepared above: PSS, 0.7g of dimethyl sulfoxide (DMSO) and 0.1g of sodium Polyacrylate (PAAS) were mixed, heated and stirred at 80 ℃ for 30 minutes to obtain PEDOT: PSS-PAAS hydrogel.
(2) The fibers were pulled out of the hydrogel with tweezers and allowed to solidify by evaporation of water, yielding PEDOT: PSS-PAH fiber. Then soaking in 70% sulfuric acid for 12 h.
Example 7
This example was used for PEDOT: preparation method of PSS-PAH fiber
(1) 3g of commercial PEDOT: PSS, 0.7g of dimethyl sulfoxide (DMSO) and 0.1g of sodium Polyacrylate (PAAS) were mixed, and stirred at 70 ℃ for 30 minutes to obtain PEDOT: PSS-PAAS hydrogel.
(2) The fibers were pulled out of the hydrogel with tweezers and allowed to solidify by evaporation of water, yielding PEDOT: PSS-PAH fibers. Then soaking in 70% sulfuric acid for 12 h.
Examples 8 to 10 are provided to illustrate the preparation method of a fibrous stretchable supercapacitor
Example 8
This example is a method for preparing a PVA-HQBQ-TsOH hydrogel electrolyte
(1) 1.5g of p-toluenesulfonic acid (TsOH), 0.03g of Hydroquinone (HQ) and 0.03g of Benzoquinone (BQ) are dissolved in a mixed solution of 5ml of water and 2.8g of acetic acid, and after uniform stirring, 0.7g of polyvinyl alcohol (PVA) is added and stirred at 85 ℃ until the PVA is completely dissolved.
Example 9
This example is for the preparation of a polymethyl acrylate solution
(1) 1g of polymethyl acrylate (PMA) was dissolved in 9g of ethyl acetate to give a 10% wt by mass fraction polymethyl acrylate solution.
Example 10
This example serves to illustrate PEDOT: preparation method of PSS-PAH super capacitor
(1) And (3) mixing PEDOT: the PSS-PAH is wrapped with hydrogel electrolyte (soaking), namely two fibers are wrapped when the fibers are dry.
(2) And coating a layer of hydrogel electrolyte on the wrapped double electrode, immersing the double electrode into 10 wt% of polymethyl acrylate solution for about 10s when the double electrode is dry, placing the immersed and coated fiber in air at room temperature to evaporate a solvent of the impregnated and coated fiber, and repeatedly immersing and airing for two to three times to complete the sealing layer of the device.
PEDOT: structural characterization of PSS-PAH fibers
Example 11
And displaying PEDOT: the visual effect and the microscopic appearance of the PSS-PAH.
See fig. 1. Figure 1 shows PEDOT prepared according to the above synthesis: PSS-PAH pictures under optical microscope showed that the fibers were very fine and uniform, about 60 μm.
See fig. 2. Figure 2 shows the results for PEDOT: PSS-PAH results of X-ray diffraction test (XDR) at 11.6 ℃ and 25.4 ℃ corresponding to PEDOT: peak of PSS. Experiments respectively test different conditions of incident light projection when the incident light projection is parallel to the fiber and when the incident light projection is vertical to the fiber, a sharper peak can be found when the incident light projection is parallel to the fiber, the fiber has stretching orientation, the parallel direction has better crystallinity, and meanwhile, the crystal promotes charge transmission in a chain and between chains, so that the fiber has a high conducting state.
See fig. 3. Figure 3 shows the results for PEDOT: PSS-PAH was subjected to Scanning Electron Microscopy (SEM) with PEDOT: cross-sectional pictures observed under SEM after freeze-drying treatment of the PSS-PAH fiber samples show the weight ratio of PEDOT: the PSS-PAH has a porous structure in cross section and has capacitance property.
PEDOT: characterization of the Properties of the PSS-PAH fibers
Example 12
And displaying PEDOT: the PSS-PAH fiber has the conductivity and the tensile property.
PSS-PAAS hydrogels were doped with varying amounts of PEDOT: PSS, for their tensile properties compared to the conductive properties. The fibers obtained from the sample doped with 2g of PEDOT to PSS are named PEDOT to PSS-PAH-1, the fibers obtained from the sample doped with 3g of PEDOT to PSS are named PEDOT to PSS-PAH-2, and the fibers obtained from the sample doped with 4g of PEDOT to PSS are named PEDOT to PSS-PAH-3.
Different PEDOT were tested with a stretcher: mechanical properties at PSS doping level, each sample was tested at a relative humidity of 45. + -. 5% with the drawing rate of the drawing machine fixed at 100 mm/min. See fig. 4. With PEDOT: the doping amount of PSS is increased, and the tensile strain tends to be gradually reduced. In the PEDOT: when the doping amount of the PSS is 4g, the elongation rate of the electrode reaches 150%, and the tensile strength of the electrode is 23MPa, which is superior to that of a plurality of flexible electrodes.
The resistance change of PEDOT PSS-PAH was monitored using a multimeter. See table 1. Table 1 shows the results obtained in different PEDOTs: PEDOT at PSS doping level: the conductivity and mechanical properties of the PSS-PAH are compared.
TABLE 1
Electrical conductivity (S m)-1) Tensile strain
PEDOT:PSS-PAH-1 1200 500%±50%
PEDOT:PSS-PAH-2 1800 300%±50%
PEDOT:PSS-PAH-3 3000 150%±50%
With PEDOT: the doping amount of the PSS is increased, and the conductivity is as high as 3000S m-1Higher than many hydrogel fibers.
During the test it was found that the fibres had very excellent water resistance and were soaked in pure water or 0.1M NaHCO3In, except for initial immersion of NaHCO3Slightly swelling in the course of time. The fibers were not damaged by soaking at 80 ℃ for 24h, see fig. 5. In FIG. 5, the left bottle is H2O, right bottle 0.1M NaHCO3This shows that the fiber has the advantages of high temperature resistance, difficult swelling and the like, and can resist water when being used as a conductive material.
PEDOT: apparent Performance and Performance characterization of PSS-PAH Fibrous Stretchable Supercapacitors (FSSCs)
Example 13
Example 13 gives PEDOT: apparent performance of PSS-PAH Fibrous Stretchable Supercapacitors (FSSC). See fig. 6. Wherein, fig. 6a is a schematic structural diagram of a fibrous supercapacitor; figure 6b shows PEDOT prepared according to example 5: macroscopic photograph of PSS-PAH Fibrous Stretchable Supercapacitor (FSSC) in which the effective length is about 1 cm. The prepared super capacitor is very light, the effective length is 1.3cm, and the weight of the super capacitor with the diameter of a single fiber being 75 mu m is only 1.141 mg.
Example 14
In this example, PEDOT prepared in example 5: PSS-PAH Fibrous Stretchable Supercapacitors (FSSC) were subjected to Cyclic Voltammetry (CV) with a change in scan rate of 5-50 mV/s. The results of the tests are shown in FIG. 7. As can be seen from the results of fig. 7, as the scan rate increases, the CV peak area increases, demonstrating that the conductivity of the electrode material is good.
See fig. 8. In fig. 8, a constant current charging and discharging (GCD) test is performed for the super capacitor, a GCD curve of different current densities is measured, and a specific capacitance is calculated according to a calculation formula of Ccell being 2 × I × t/(U × V), wherein I represents the magnitude of the current value of the discharge, t represents the length of the discharge time, V represents the effective volume of the whole device, and U represents the size of the test window of the voltage. As can be seen from the results, the maximum specific capacitance is a current density of 0.87A/cm3When the capacitance value of the device is up to 67.4F/cm3And the surface capacitance can reach 100mF/cm2
For PEDOT: the PSS-PAH Fibrous Stretchable Supercapacitor (FSSC) was subjected to the cycling stability test, the test results of this example, see FIG. 9.
As shown in FIG. 9, it can be seen that the concentration is 0.67A/cm3The capacity retention ratio after 8000 charge-discharge cycles was 99%.
Example 15
To test the change in specific capacitance under tension, a Fibrous Stretchable Supercapacitor (FSSC) was mounted on a stretcher jig, stretched to 140% step-wise with 20% strain (stretching rate 50mm/min), while the changes in Cyclic Voltammetry (CV) and galvanostatic charge-discharge (GCD) tests were monitored during stretching using an electrochemical meter 660I test.
See fig. 10. Wherein, fig. 10a is the capacity retention under tensile strain; fig. 10b shows the capacitance retention during cycling.
The CV curve and the GCD graph have almost no change under different strains, which indicates that the electrochemical properties are hardly affected by stretching, and the specific capacitance retention is calculated to be 100%, as shown in fig. 10 a. The supercapacitor is directly stretched to 100% and released under the speed of 50mm/min in a stretching machine, the stretching-releasing cycle is 1000 circles, and meanwhile, the electrochemical instrument 660I is used for testing and monitoring the specific capacitance change, as shown in figure 10b, the capacitance retention rate is 83%.
PEDOT: practical application of PSS-PAH Fibrous Stretchable Supercapacitors (FSSC).
The diodes 40s can be lit up by connecting four supercapacitors in series with copper glue and silver glue, see fig. 11. If two sets of series connected devices are connected in parallel, the clock can be powered for 1 minute, see fig. 12.
The above detailed description of a composite fibrous material and method of making the same, and a high-stretchability fibrous supercapacitor, provided by the present invention, and the principles and embodiments of the present invention are described herein using specific examples, which are provided only to facilitate an understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. The composite fiber material is characterized by comprising a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer and sodium polyacrylate compounded in the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer.
2. The composite fiber material according to claim 1, wherein the mass ratio of the total mass of the poly 3, 4-ethylenedioxythiophene and polystyrene sulfonate to the sodium polyacrylate in the composite fiber material is 1: (0.025-0.05);
the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate polymer is a conjugated polymer;
the conjugated polymer includes a rigid conductive conjugated polymer.
3. The composite fibrous material according to claim 1, wherein the composite fibrous material is a hydrogel fibrous material;
the length of the composite fiber material is 3-30 cm;
the diameter of the composite fiber material is 30-300 mu m;
the compounding includes physical compounding.
4. The composite fiber material of claim 1, wherein the composite fiber material has a porous structure;
the aperture of the composite fiber material is 0.25-2 μm;
the composite fiber material is a high-stretchability conductive composite fiber material;
the elongation at break of the composite fiber material is 50-500%;
the conductivity of the composite fiber material is 1000-3000 Sm-1
The composite fiber material is a water-resistant composite fiber material.
5. The preparation method of the composite fiber material is characterized by comprising the following steps of:
1) mixing 3, 4-ethylenedioxythiophene, polystyrene sulfonic acid and water, adding ferric sulfate and sodium persulfate, reacting, and washing to obtain poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate composite gel;
2) heating and mixing the poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate composite gel obtained in the step, sodium polyacrylate and a solvent to obtain a poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate hydrogel;
3) and (3) performing stretch spinning on the poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate hydrogel obtained in the step, and curing to obtain the poly-3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber material.
6. The preparation method according to claim 5, wherein the mass ratio of the 3, 4-ethylenedioxythiophene to the polystyrene sulfonic acid is (0.15-0.25): 1;
the molar ratio of the 3, 4-ethylenedioxythiophene to the ferric sulfate is (1.0-2.0): 1;
the molar ratio of the sodium persulfate to the 3, 4-ethylenedioxythiophene is (0.8-1.5): 1;
the reaction time is 12-24 h;
the washing is specifically to wash until the supernatant is neutral.
7. The method of claim 5, wherein the solvent comprises one or more of dimethylsulfoxide, acetone, N-dimethylformamide, acetonitrile, methanol, and ethanol;
the heating and mixing temperature is 50-90 ℃;
the heating and mixing time is 20-60 min;
the curing is specifically that the water is evaporated and then cured;
the curing process also comprises an acid soaking treatment;
the acid soaking time is 6-24 hours.
8. A supercapacitor, comprising at least 2 wound fibrous materials;
the fiber material comprises a composite fiber material and a hydrogel electrolyte coated on the surface of the composite fiber material;
the composite fiber material is the composite fiber material as set forth in any one of claims 1 to 4 or the composite fiber material prepared by the preparation method as set forth in any one of claims 5 to 7.
9. The supercapacitor according to claim 8, further comprising a second layer of hydrogel electrolyte layer wrapped on the surface of the wound fibrous material;
after the second hydrogel electrolyte layer is wrapped, no gap exists among the 2 wound fiber materials;
the super capacitor also comprises a protective layer coated on the second hydrogel electrolyte layer;
the protective layer is made of one or more of polymethyl acrylate, polybutyl acrylate, polydimethylsiloxane and polyethyl acrylate;
the super capacitor is a fibrous stretchable super capacitor;
the super capacitor comprises an all-solid-state super capacitor.
10. The supercapacitor of claim 9, wherein the hydrogel electrolyte comprises a polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte;
the total mass content of hydroquinone and benzoquinone in the hydrogel electrolyte is 0.1-1%;
the preparation method of the polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte comprises the following steps:
mixing p-toluenesulfonic acid, hydroquinone, benzoquinone, water and acetic acid, adding polyvinyl alcohol, heating and mixing to obtain a polyvinyl alcohol-hydroquinone-benzoquinone-p-toluenesulfonic acid hydrogel electrolyte;
the temperature for heating and mixing is 80-100 ℃;
the preparation method of the supercapacitor comprises the following steps:
two poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber materials are soaked in hydrogel electrolyte, after the two poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber materials are taken out, the two fiber materials are wrapped when the two poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber materials are to be dried, the hydrogel electrolyte is compounded on the surfaces of the wrapped fiber materials, a protective layer is compounded when the two poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber materials are to be dried, and the supercapacitor is obtained after the two poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate-sodium polyacrylate composite fiber materials are dried.
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